EP1572855B1 - Sodium percarbonate particles with improved storage stability - Google Patents
Sodium percarbonate particles with improved storage stability Download PDFInfo
- Publication number
- EP1572855B1 EP1572855B1 EP03813896A EP03813896A EP1572855B1 EP 1572855 B1 EP1572855 B1 EP 1572855B1 EP 03813896 A EP03813896 A EP 03813896A EP 03813896 A EP03813896 A EP 03813896A EP 1572855 B1 EP1572855 B1 EP 1572855B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sodium percarbonate
- percarbonate particles
- finely divided
- sodium
- particles according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 title claims abstract description 149
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 title claims abstract description 138
- 229940045872 sodium percarbonate Drugs 0.000 title claims abstract description 138
- 238000003860 storage Methods 0.000 title abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 84
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 239000003599 detergent Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000007844 bleaching agent Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000001698 pyrogenic effect Effects 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910002012 AerosilĀ® Inorganic materials 0.000 description 23
- 239000010410 layer Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 230000002209 hydrophobic effect Effects 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 11
- 238000004061 bleaching Methods 0.000 description 10
- 239000012459 cleaning agent Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- -1 alkali metal percarbonate Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005253 cladding Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910002016 AerosilĀ® 200 Inorganic materials 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 108010005774 beta-Galactosidase Proteins 0.000 description 1
- 102000005936 beta-Galactosidase Human genes 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002477 conductometry Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
- C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/38—Preparation in the form of granules, pieces or other shaped products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Definitions
- the invention relates to sodium percarbonate particles having improved storage stability in the presence of builders, especially in the presence of silicatic builders.
- Sodium percarbonate is used as a bleaching agent and as a bleaching effective ingredient in laundry detergents and cleaners.
- Sodium percarbonate has the disadvantage that it tends to decompose in the presence of builders, which can absorb moisture and released again, resulting in a loss of active oxygen and thus bleaching effect.
- sodium percarbonate is therefore preferably used in the form of particles with a stabilizing coating layer in order to achieve improved storage stability.
- sodium percarbonate powder can be stabilized by dry admixing of pyrogenic oxides, preferably fumed silica, in amounts of about 1%.
- pyrogenic oxides preferably fumed silica
- the stabilization achievable in this way is not yet sufficient to avoid the decomposition of sodium percarbonate in mixtures with silicatic builders.
- US Pat. No. 4,215,990 describes builder-free bleaching agents which, in addition to 5 to 50% by weight of sodium percarbonate, also contain 0.1 to 2% by weight of a finely divided silica having a particle size in the range from 1 to 150 ā m. to In order to avoid caking, the bleaching agents additionally contain 0.05 to 1% by weight of corn starch and / or diethyl phthalate.
- the document contains no reference to the use of hydrophobized silica or the stability of the bleaches described in the presence of builders.
- WO 92/07057 describes liquid detergent compositions containing a solid water-soluble peroxygen compound, a surfactant and a hydrophobic silica. These detergent compositions contain from 0.5% to 5% by weight of the hydrophobic silica, as well as the peroxygen compound in an amount providing from 0.5% to 3% by weight of active oxygen. The addition of the hydrophobic silica causes thickening of the liquid detergent composition, from which it can be seen that the hydrophobic silica is dispersed in the liquid phase of the detergent composition.
- US 5,374,368 and US 5,496,542 describe hydrogen peroxide-releasing preparations in liquid or in gel form, which in addition to 55 to 90 wt .-% of polyalkylene glycol and 5 to 20 wt .-% sodium percarbonate also 0.5 to 3 wt .-% and 0.5 to Contain 6 wt .-% colloidal silica.
- Another suitable colloidal silica is the hydrophobized silica AerosilĀ® R972. Again, the silica acts as a thickener for the polyalkylene glycol and is therefore dispersed in the liquid phase of the preparation.
- WO 95/02724 describes detergent granules containing an alkali metal percarbonate having an average particle size in the range of 250 to 900 microns and a hydrophobic material selected from silicic acid, talc, zeolite, DAY and hydrotalcite in a weight ratio in the range of 4: 1 to 40: 1 included.
- the hydrophobic material used is preferably a hydrophobicized silica such as AerosilĀ® R972.
- the hydrophobic material is dusted onto the percarbonate particles, this step being carried out in a rotating drum, a mixer or a fluidized bed.
- the described detergent granules have an improved stability of the percarbonate against decomposition even in the presence of builders.
- WO 95/02724 teaches on page 2 in the fourth paragraph that the described weight ratio of alkali metal percarbonate to hydrophobic material in the range of 4: 1 to 40: 1 is an essential feature to achieve improved storage stability of the percarbonate in the described detergent compositions.
- sodium percarbonate particles to which a hydrophobized silica has been dusted in this quantitative ratio have disadvantages in their handling as well as in their use in bleaches, detergents and cleaners in comparison with commercially available sodium percarbonate products which do not contain hydrophobicized silica.
- When handling the sodium percarbonate particles there is an increased formation of dust, which complicates the pneumatic transport of the particles and further processing in the production of bleach, detergents or cleaning agents.
- sodium percarbonate particles which have been dusted with hydrophobized silica and described in WO 95/02724 are also less readily dispersible in water and tend to form lumps and to deposit the added ones hydrophobized silica on the water surface.
- the use of these sodium percarbonate particles in bleaching, washing and cleaning agents therefore leads to a deterioration of the application properties of these agents.
- the object of the invention was therefore to provide sodium percarbonate particles which have a high storage stability in the presence of builders and at the same time can be handled and stored without dust formation and without caking of the particles.
- the sodium percarbonate particles must also be easy to disperse in water without residues, so that their use in bleaching, washing and cleaning agents does not lead to a deterioration in the application properties of these agents.
- the present invention relates to sodium percarbonate particles, characterized in that they contain on their surface 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of a hydrophobized finely divided oxide of the elements silicon, aluminum or titanium or a Mixed oxide contain these elements, wherein the hydrophobicized finely divided oxide is preferably a hydrophobized fumed or precipitated silica.
- the invention additionally encompasses a process for the preparation of these sodium percarbonate particles, which comprises sodium percarbonate particles, which optionally have one or more coating layers, with 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight, of a hydrophobized one of finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements are mixed, wherein the sodium percarbonate particles used are preferably mixed in a dry state with the hydrophobized finely divided oxide.
- the invention also encompasses the use of the sodium percarbonate particles according to the invention as bleaching component in a bleach, detergent or cleaning agent.
- the sodium percarbonate particles according to the invention contain on their surface 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of a hydrophobized finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements. Preferably, they contain as hydrophobized finely divided oxide, a hydrophobized fumed or precipitated silica.
- Suitable finely divided oxides are, for example, pyrogenic oxides which are obtained by flame hydrolysis of volatile compounds of the elements silicon, aluminum or titanium or of mixtures of these compounds.
- the pyrogenic oxides or mixed oxides obtainable in this way preferably have an average primary particle size of less than 50 nm and can lead to larger particles be aggregated, the average particle size is preferably less than 20 microns.
- precipitated oxides which have been precipitated from aqueous solutions of compounds of the elements silicon, aluminum or titanium or mixtures of these compounds.
- the precipitated oxides, or mixed oxides, in addition to silicon, aluminum and titanium may still contain small amounts of alkali metal or alkaline earth metal ions.
- the mean particle size of the precipitated oxides is preferably less than 50 microns and more preferably less than 20 microns.
- Hydrophobised oxides in the context of the invention are oxides which have organic radicals bound to their surface via chemical compounds and are not wetted by water. Hydrophobic oxides can be prepared, for example, by reacting fumed or precipitated oxides with organosilanes, silazanes or polysiloxanes. Suitable silicon compounds for the preparation of hydrophobized oxides are known from EP-A 0 722 992, page 3, line 9 to page 6, line 6. Hydrophoborated oxides which have been prepared by reacting a finely divided oxide with a silicon compound of the compound classes (a) to (e) and (k) to (m) mentioned in EP-A 0 722 992 are particularly preferred. The hydrophobized finely divided oxides preferably have a methanol wettability of at least 40.
- the sodium percarbonate particles according to the invention preferably have an average particle size in the range from 0.2 to 5 mm and particularly preferably in the range from 0.5 to 2 mm. Preference is given to sodium percarbonate particles a low fines content, preferably with a proportion of less than 10 wt .-% particles smaller than 0.2 mm and more preferably less than 10 wt .-% of particles having a particle size of less than 0.3 mm.
- the sodium percarbonate particles according to the invention preferably have a substantially spherical shape with a smooth surface.
- Particles with a smooth surface have a surface roughness of less than 10% of the particle diameter, and preferably less than 5% of the particle diameter.
- the sodium percarbonate particles according to the invention can be prepared starting from sodium percarbonate particles which have been produced by one of the known production processes for sodium percarbonate.
- a suitable production process for sodium percarbonate is the crystallization of sodium percarbonate from aqueous solutions of hydrogen peroxide and sodium carbonate, wherein the crystallization can be carried out both in the presence and in the absence of a salting out agent, by way of example reference is made to EP-A 0 703 190.
- suitable is the fluidized-bed spray granulation by spraying aqueous hydrogen peroxide solution and aqueous sodium carbonate solution onto sodium percarbonate nuclei in a fluidized bed with simultaneous evaporation of water, by way of example reference is made to WO 95/06615.
- the reaction of solid sodium carbonate with an aqueous hydrogen peroxide solution and subsequent drying is also a suitable production process.
- the sodium percarbonate particles produced by one of these processes consist essentially of sodium carbonate perhydrate of the composition 2Na 2 CO 3 .3H 2 O 2 . You can go beyond that still small amounts of known stabilizers for peroxygen compounds, such as magnesium salts, silicates, phosphates and / or chelating agents.
- percarbonate particles produced by the crystallization process in the presence of a salting-out agent may also contain small amounts of the salting-out agent used, such as, for example, sodium chloride.
- the sodium percarbonate particles according to the invention are preferably prepared starting from sodium percarbonate particles obtained by fluidized-bed spray granulation.
- the sodium percarbonate particles on a core of sodium percarbonate additionally have a coating layer which contains one or more inorganic hydrate-forming salts as the main constituent.
- the inorganic or hydrate-forming salts are preferably selected from the series sodium sulfate, sodium carbonate, sodium bicarbonate or magnesium sulfate, as well as mixtures of these compounds and / or mixed salts of these compounds. Particularly preferred as the inorganic hydrate-forming salt is sodium sulfate.
- the cladding layer consists essentially of sodium sulfate. The proportion of this coating layer on the sodium percarbonate particle is preferably in the range from 1 to 20% by weight and more preferably in the range from 2 to 10% by weight, calculated for the non-hydrated form of the hydrate-forming salts.
- the coating of the sodium percarbonate particles takes place in a manner known per se.
- the particles to be coated are mixed as uniformly as possible with a solution containing one or more shell components contacted and dried simultaneously or subsequently.
- the contacting may take place on a granulating dish or in a mixer, such as a tumbling mixer.
- the coating is preferably carried out by fluidized-bed coating, in which case an aqueous solution of the inorganic hydrate-forming salts is sprayed onto the sodium percarbonate particles suspended in a fluidized bed or with sodium percarbonate particles coated with one or more layers and dried simultaneously with the fluidized-bed gas.
- Fluidized bed gas may be any gas, particularly air, air directly heated with a combustion gas having a CO 2 content in the range of, for example, 0.1 to about 15%, pure CO 2 , nitrogen and inert gases.
- the coating layer is particularly preferably applied by the method described in EP-A 0 970 917.
- the shell layer of inorganic hydrate-forming salts is preferably applied so as to completely surround the core of sodium percarbonate.
- the cladding layer is applied in the form of an aqueous solution, by dissolving the sodium percarbonate particles during coating at the boundary between core material and cladding layer material, a boundary region can form which can contain other compounds in addition to sodium percarbonate and the cladding layer material.
- this boundary region may contain sodium hydrogen carbonate and also double salts of sodium bicarbonate and sodium sulfate such as sesquicarbonate or Wegscheiders salt when applying a coating layer of substantially sodium sulfate in addition to sodium percarbonate and sodium sulfate.
- the coating layer of inorganic hydrate-forming salts can be applied directly to the core of sodium percarbonate be or be underlain by one or more other enveloping layers. In addition, it may be superposed by one or more further cladding layers.
- the second cladding layer consists essentially of alkali metal silicate.
- Alkali metal silicate is to be understood as meaning all alkali metal silicates which give on average the abovementioned module.
- the modulus is the molar ratio of SiO 2 to M 2 O, where M is an alkali metal and is preferably lithium, sodium or potassium or a mixture of these alkali metals.
- Particularly preferred is sodium silicate.
- the modulus of the alkali metal silicate is preferably in the range of 3 to 5, and more preferably in the range of 3.2 to 4.2.
- the proportion of the second shell layer to the sodium percarbonate particles is preferably in the range of 0.2 to 3 wt .-%.
- the second coating layer is preferably applied by spraying on an aqueous solution containing alkali metal silicate, wherein preferably an aqueous solution having a concentration of alkali metal silicate in the range from 2 to 20 wt .-%, particularly preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% is used.
- a so-called water glass solution is preferably sprayed on.
- the sodium percarbonate particles according to the invention exhibit improved storage stability in the presence of builders compared to comparable sodium percarbonate particles which do not contain a hydrophobized finely divided oxide on the surface, in particular in the presence of silicatic builders, e.g. Zeolites.
- silicatic builders e.g. Zeolites.
- the same storage stability can be achieved with a much smaller amount of shell layer in the sodium percarbonate particles according to the invention, than with comparable particles which contain no hydrophobized finely divided oxide on the surface.
- the same stabilities can already be achieved with an amount of 2% by weight of coating layer as in the case of sodium percarbonate particles without hydrophobized finely divided oxide on the surface only with a coating layer amount of 6% by weight. -% be achieved.
- the sodium percarbonate particles according to the invention having a shell layer of an inorganic hydrate-forming salt can therefore be prepared with the same storage stability with a higher active oxygen content.
- the sodium percarbonate particles according to the invention have a reduced tendency to cake in comparison to particles which contain no hydrophobic finely divided oxide on the surface, in particular when stored under pressure.
- the sodium percarbonate particles according to the invention are therefore easy to ensile, ie they can be stored in silos for a long time and, even after prolonged storage in the silo, exhibit good flow behavior without formation of lumps or caking in the silo.
- the advantage of reduced tendency to cake is particularly pronounced in the case of sodium percarbonate particles according to the invention, which have a second coating layer over an outer layer containing an inorganic hydrate-forming salt, which contains an alkali metal silicate as the main component.
- the sodium percarbonate particles according to the invention exhibit a significantly lower dust formation during handling, since the hydrophobized finely divided oxide in the sodium percarbonate particles according to the invention Surprisingly firmly adheres to the surface of the sodium percarbonate particles and virtually does not contribute to abrasion and dust formation.
- the sodium percarbonate particles according to the invention can therefore be transported by pneumatic conveying, without the formation of dust and increased abrasion or segregation of sodium percarbonate and hydrophobic finely divided oxide.
- the sodium percarbonate particles according to the invention show virtually no disadvantages in the dispersibility in water in comparison with sodium percarbonate particles which contain no hydrophobized finely divided oxide on the surface.
- the sodium percarbonate particles according to the invention dissolve just as quickly in water as sodium percarbonate particles which contain no hydrophobized finely divided oxide and do not lead to disruptive precipitations of the hydrophobized finely divided oxide when dissolved in water in the usual amounts used in bleaching, washing and cleaning agents.
- the invention furthermore relates to a process for the preparation of the sodium percarbonate particles according to the invention, in which sodium percarbonate particles optionally having one or more shell layers contain from 0.01 to 1% by weight and preferably from 0.1 to 0.5% by weight of a hydrophobicized finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements are mixed.
- the hydrophobized finely divided oxide used is preferably a hydrophobized pyrogenic or precipitated silica.
- the sodium percarbonate particles used preferably have an average particle size in the range from 0.2 to 5 mm and particularly preferably in the range from 0.5 to 2 mm.
- the hydrophobized finely divided oxide preferably has an average particle size of less than 20 ā m.
- the ratio of the mean particle size of the sodium percarbonate particles used to the mean particle size of the hydrophobized finely divided oxide used is preferably greater than 20 and particularly preferably greater than 50.
- the sodium percarbonate particles used are preferably mixed in the dry state with the hydrophobized finely divided oxide.
- the mixture can be carried out in all apparatuses suitable for the mixing of solids.
- the sodium percarbonate particles are dispersed in a gas phase for mixing with the hydrophobized finely divided oxide.
- the mixing process can take place, for example, in a fluidized bed, in a downpipe or in a downflow conveyor.
- the hydrophobized finely divided oxide is almost completely bound to the surface of the sodium percarbonate particles used so that the finely divided oxide used is virtually free of fine grain and dust formation contributes to the product obtained.
- the mixing of the sodium percarbonate particles used with the hydrophobized finely divided oxide in a downpipe or in an airflow conveyor makes it easy to continuously produce the sodium percarbonate particles according to the invention and does not require mixing devices with additional moving parts.
- the continuous mixing in a downpipe or a downdraft conveyor makes it possible to produce a particularly homogeneous product in which essentially all sodium percarbonate particles have on their surface the proportion by weight of a hydrophobized finely divided oxide according to the invention.
- FIGS. 1 and 2 show scanning electron micrographs of sodium percarbonate particles according to the invention with a coating layer of 6% by weight of sodium sulfate, which contain 0.5% by weight of the hydrophobized silica AerosilĀ® R812 on the surface.
- the particles were prepared by fluidized bed spray granulation followed by coating by spraying sodium sulfate solution in a fluidized bed to evaporate water and dry mixing the coated particles with the hydrophobized silica in a tumble mixer.
- the Figures show that in the particles according to the invention the hydrophobized silica adheres almost completely to the surface of the sodium percarbonate particles used.
- Another object of the invention is directed to the use of sodium percarbonate according to the invention as a bleach-active component, in detergents, bleaches or cleaning agents.
- the washing, bleaching or cleaning agents are in particular those which contain at least one builder and preferably a silicate builder.
- Builders are understood to be all soluble or insoluble compounds which, when using the washing, bleaching or cleaning agent, are capable of sequestering or complexing calcium and / or magnesium ions from the water used.
- Examples of silicate builders are soluble silicates, insoluble phyllosilicates and zeolites, in particular zeolite A and zeolite X.
- sodium percarbonate particles according to the invention as a bleach-acting component in detergents, bleaches or cleaners improves the storage stability of these compositions and reduces the loss of active oxygen during storage of the compositions.
- the sodium percarbonate used in the examples for the preparation of the sodium percarbonate particles according to the invention was prepared by fluidized-bed granulation according to the process described in WO 95/06615.
- the sodium percarbonate particles used had a mean particle size of 0.65 mm and contained virtually no particles with a diameter of less than 0.3 mm.
- Sodium percarbonate particles having a coating layer of 2% by weight of sodium sulfate were prepared therefrom in a laboratory apparatus by spraying aqueous sodium sulfate solution and simultaneously evaporating water.
- Sodium percarbonate particles with a coating layer of 6% by weight sodium sulfate were prepared by spraying an aqueous sodium sulfate solution according to the method described in EP-A 0 670 917.
- Tables 1 to 3 show that the sodium percarbonate particles according to the invention have a markedly better storage stability in the presence of zeolitic builders than sodium percarbonate particles which do not have on their surface a finely divided oxide or a finely divided hydrophilic silica, such as AerosilĀ® 200 or SipernatĀ® 22S included.
- Table 1 Storage stability of sodium percarbonate without coating layer in the presence of zeolite A ā / i> Ex. Finely divided oxide Amount of finely divided oxide in% by weight Rel.
- Finely divided oxide Amount of finely divided oxide in% by weight Rel. Remainder Oa in% 15 * without 85 16 Aerosil R812 0.1 90 17 Aerosil R812 0.3 95 18 Aerosil R972 0.1 89 19 * Aerosil R972 2.5 91 * not inventive example
- the active oxygen contents and the handling properties of the dissolution time and the abrasion are compiled.
- the active oxygen contents were determined by manganometric titration.
- the dissolution time was determined by conductometry as the time at which 90% of the final conductivity value is achieved by dissolving 2.5 g of product per liter of water at 20 Ā° C. with stirring.
- the abrasion was determined according to ISO 5937.
- the product of Examples 6, 10, 16 and 18 showed no tendency to clump in the determination of the dissolution time and provided clear solutions.
- the product of Example 19 clumped in determining the dissolution time and showed visible deposition of the hydrophobic silica even after complete dissolution of the sodium percarbonate on the surface of the solution.
- Table 5 shows by sieve analyzes certain grain size distributions of the samples from Examples 6 and 10, wherein the sample of Example 10 differs from the sample of Example 6 only by the application of 0.3 wt .-% AerosilĀ® R812.
- the absence of fine grain in the range of less than 0.3 mm shows that the applied AerosilĀ® adheres to the surface of the sodium percarbonate particles.
- the fluidity index ffc is a measure of the fluidity of the material after storage under pressure, as it occurs when stored in a silo. Materials with a higher flow index ffc show and are also less time-hardening and fewer caking after prolonged storage in a silo still free-flowing.
- Table 7 summarizes the results of climate tests for determining the storage stability of sodium percarbonate in a commercial heavy-duty detergent.
- the sodium percarbonate is mixed with a phosphate-free zeolite-containing detergent powder and with TAED activator in an amount such that the mixture contains 5% by weight of TAED and the active oxygen content of the mixture is about 2.35% by weight.
- the detergent powder contains as ingredients (in% by weight) Anionic surfactants 12
- Nonionic surfactants 8th Zeolite A 36 soda 10 sodium silicates 3 Remainder (including humidity) 31 800 g of the mixture are stored in commercially available, water-repellent impregnated and bonded E1 detergent packages at 35 Ā° C and 80% relative humidity in the climatic chamber.
- a package is taken and the active oxygen content is determined manganometrically in the usual way. From the determined Oa content and the starting Oa content, the relative residual Oa is calculated after 4 and 8 weeks, respectively.
- Example 20 was carried out with a sodium percarbonate having a coating layer of 6 wt .-% sodium sulfate and a particle size of more than 0.4 mm.
- Example 21 was carried out with sodium percarbonate particles according to the invention, in which, as described above, 0.5% by weight of the hydrophobized silica AerosilĀ® R812 was applied to the sodium percarbonate particles of Example 20.
- Table 7 Storage stability of sodium percarbonate in a heavy-duty detergent ā / i> Ex. Finely divided oxide rel. Residual Oa after 4 weeks in% rel. Residual oa after 8 weeks in% 20 * without 95 86 21 0.5% by weight Aerosil R812 98 88 * not inventive example
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Abstract
Description
Die Erfindung betrifft Natriumpercarbonatpartikel mit verbesserter LagerstabilitƤt in Gegenwart von Buildern, insbesondere in Gegenwart von silikatischen Buildern.The invention relates to sodium percarbonate particles having improved storage stability in the presence of builders, especially in the presence of silicatic builders.
Natriumpercarbonat wird als Bleichmittel und als bleichwirksamer Bestandteil in Wasch- und Reinigungsmitteln verwendet. Natriumpercarbonat weist dabei den Nachteil auf, dass es in Gegenwart von Buildern, die Feuchtigkeit aufnehmen und wieder abgegeben kƶnnen, zur Zersetzung neigt, was zu einem Verlust an Aktivsauerstoff und damit an Bleichwirkung fĆ¼hrt. FĆ¼r die Anwendung in builderhaltigen Bleichmitteln, Waschmitteln oder Reinigungsmitteln wird Natriumpercarbonat deshalb vorzugsweise in Form von Partikeln mit einer stabilisierenden HĆ¼llschicht eingesetzt, um eine verbesserte LagerstabilitƤt zu erzielen.Sodium percarbonate is used as a bleaching agent and as a bleaching effective ingredient in laundry detergents and cleaners. Sodium percarbonate has the disadvantage that it tends to decompose in the presence of builders, which can absorb moisture and released again, resulting in a loss of active oxygen and thus bleaching effect. For use in builder-containing bleaches, detergents or cleaning agents, sodium percarbonate is therefore preferably used in the form of particles with a stabilizing coating layer in order to achieve improved storage stability.
Aus DE 870 092 ist bekannt, dass sich Natriumpercarbonatpulver durch trockenes Zumischen von pyrogenen Oxiden, vorzugsweise pyrogener KieselsƤure, in Mengen von etwa 1 % stabilisieren lƤsst. Die auf diesem Weg erreichbare Stabilisierung ist jedoch noch nicht ausreichend, um die Zersetzung von Natriumpercarbonat in Mischungen mit silikatischen Buildern zu vermeiden.From DE 870 092 it is known that sodium percarbonate powder can be stabilized by dry admixing of pyrogenic oxides, preferably fumed silica, in amounts of about 1%. However, the stabilization achievable in this way is not yet sufficient to avoid the decomposition of sodium percarbonate in mixtures with silicatic builders.
US 4,215,990 beschreibt Builder-freie Bleichmittel, die neben 5 bis 50 Gew.-% Natriumpercarbonat noch 0,1 bis 2 Gew.-% einer feinteiligen KieselsƤure mit einer PartikelgrƶĆe im Bereich von 1 bis 150 Āµm enthalten. Zur Vermeidung von Verbackung enthalten die Bleichmittel zusƤtzlich 0,05 bis 1 Gew.-% MaisstƤrke und/oder Diethylphthalat. Das Dokument enthƤlt keinen Hinweis auf die Verwendung von hydrophobierter KieselsƤure oder die StabilitƤt der beschriebenen Bleichmittel in Gegenwart von Buildern.US Pat. No. 4,215,990 describes builder-free bleaching agents which, in addition to 5 to 50% by weight of sodium percarbonate, also contain 0.1 to 2% by weight of a finely divided silica having a particle size in the range from 1 to 150 Ī¼m. to In order to avoid caking, the bleaching agents additionally contain 0.05 to 1% by weight of corn starch and / or diethyl phthalate. The document contains no reference to the use of hydrophobized silica or the stability of the bleaches described in the presence of builders.
WO 92/07057 beschreibt flĆ¼ssige Waschmittelzusammensetzungen, die eine feste wasserlƶsliche Persauerstoffverbindung, ein Tensid und eine hydrophobe KieselsƤure enthalten. Diese Waschmittelzusammensetzungen enthalten 0,5 bis 5 Gew.-% der hydrophoben KieselsƤure, sowie die Persauerstoffverbindung in einer Menge, die 0,5 bis 3 Gew.-% Aktivsauerstoff zur VerfĆ¼gung stellt. Der Zusatz der hydrophoben KieselsƤure bewirkt eine Verdickung der flĆ¼ssigen Waschmittelzusammensetzung, woraus ersichtlich ist, dass die hydrophobe KieselsƤure in der FlĆ¼ssigphase der Waschmittelzusammensetzung dispergiert vorliegt.WO 92/07057 describes liquid detergent compositions containing a solid water-soluble peroxygen compound, a surfactant and a hydrophobic silica. These detergent compositions contain from 0.5% to 5% by weight of the hydrophobic silica, as well as the peroxygen compound in an amount providing from 0.5% to 3% by weight of active oxygen. The addition of the hydrophobic silica causes thickening of the liquid detergent composition, from which it can be seen that the hydrophobic silica is dispersed in the liquid phase of the detergent composition.
US 5,374,368 und US 5,496,542 beschreiben Wasserstoffperoxid freisetzende Zubereitungen in flĆ¼ssiger oder in Gelform, die neben 55 bis 90 Gew.-% Polyalkylenglykol und 5 bis 20 Gew.-% Natriumpercarbonat auch 0,5 bis 3 Gew.-% bzw. 0,5 bis 6 Gew.-% kolloidale KieselsƤure enthalten. Als geeignete kolloidale KieselsƤure ist auch die hydrophobierte KieselsƤure AerosilĀ® R972 genannt. Auch hier wirkt die KieselsƤure als Verdickungsmittel fĆ¼r das Polyalkylenglykol und ist demnach in der FlĆ¼ssigphase der Zubereitung dispergiert.US 5,374,368 and US 5,496,542 describe hydrogen peroxide-releasing preparations in liquid or in gel form, which in addition to 55 to 90 wt .-% of polyalkylene glycol and 5 to 20 wt .-% sodium percarbonate also 0.5 to 3 wt .-% and 0.5 to Contain 6 wt .-% colloidal silica. Another suitable colloidal silica is the hydrophobized silica AerosilĀ® R972. Again, the silica acts as a thickener for the polyalkylene glycol and is therefore dispersed in the liquid phase of the preparation.
WO 95/02724 beschreibt Waschmittelgranulate, die ein Alkalimetallpercarbonat mit einer mittleren PartikelgrƶĆe im Bereich von 250 bis 900 Āµm und ein hydrophobes Material ausgewƤhlt aus KieselsƤure, Talk, Zeolith, DAY und Hydrotalcit in einem GewichtsverhƤltnis im Bereich von 4 : 1 bis 40 : 1 enthalten. Als hydrophobes Material wird bevorzugt eine hydrophobierte KieselsƤure, wie z.B. AerosilĀ® R972 verwendet. In einer beschriebenen AusfĆ¼hrungsform zur Herstellung der Waschmittelzubereitung wird das hydrophobe Material auf die Percarbonatpartikel aufgestƤubt, wobei dieser Schritt in einer rotierenden Trommel, einem Mischer oder einer Wirbelschicht durchgefĆ¼hrt wird. Die beschriebenen Waschmittelgranulate weisen eine verbesserte StabilitƤt des Percarbonats gegen Zersetzung auch in Gegenwart von Buildern auf.WO 95/02724 describes detergent granules containing an alkali metal percarbonate having an average particle size in the range of 250 to 900 microns and a hydrophobic material selected from silicic acid, talc, zeolite, DAY and hydrotalcite in a weight ratio in the range of 4: 1 to 40: 1 included. The hydrophobic material used is preferably a hydrophobicized silica such as AerosilĀ® R972. In a described embodiment for producing the detergent preparation, the hydrophobic material is dusted onto the percarbonate particles, this step being carried out in a rotating drum, a mixer or a fluidized bed. The described detergent granules have an improved stability of the percarbonate against decomposition even in the presence of builders.
WO 95/02724 lehrt auf Seite 2 im vierten Absatz, dass das beschriebene GewichtsverhƤltnis von Alkalimetallpercarbonat zu hydrophobem Material im Bereich von 4 : 1 bis 40 : 1 ein wesentliches Merkmal ist, um in den beschriebenen Waschmittelzusammensetzungen eine verbesserte LagerstabilitƤt des Percarbonats zu erreichen. Natriumpercarbonatpartikel, auf die eine hydrophobierte KieselsƤure in diesem MengenverhƤltnis aufgestƤubt wurde, weisen jedoch im Vergleich zu handelsĆ¼blichen Natriumpercarbonatprodukten, die keine hydrophobierte KieselsƤure enthalten, Nachteile in ihrer Handhabung, sowie bei ihrer Verwendung in Bleich-, Wasch- und Reinigungsmitteln auf. Bei der Handhabung der Natriumpercarbonatpartikel kommt es zu einer verstƤrkten Staubbildung, was die pneumatische Fƶrderung der Partikel und die Weiterverarbeitung in der Herstellung von Bleich-, Wasch- oder Reinigungsmitteln erschwert. Die in WO 95/02724 beschriebenen, mit hydrophobierter KieselsƤure bestƤubten Natriumpercarbonatpartikel lassen sich darĆ¼ber hinaus auch schlechter in Wasser dispergieren und neigen zur Bildung von Verklumpungen und zur Abscheidung der zugesetzten hydrophobierten KieselsƤure auf der WasseroberflƤche. Die Verwendung dieser Natriumpercarbonatpartikel in Bleich-, Wasch- und Reinigungsmitteln fĆ¼hrt deshalb zu einer Verschlechterung der Anwendungseigenschaften dieser Mittel.WO 95/02724 teaches on page 2 in the fourth paragraph that the described weight ratio of alkali metal percarbonate to hydrophobic material in the range of 4: 1 to 40: 1 is an essential feature to achieve improved storage stability of the percarbonate in the described detergent compositions. However, sodium percarbonate particles to which a hydrophobized silica has been dusted in this quantitative ratio have disadvantages in their handling as well as in their use in bleaches, detergents and cleaners in comparison with commercially available sodium percarbonate products which do not contain hydrophobicized silica. When handling the sodium percarbonate particles, there is an increased formation of dust, which complicates the pneumatic transport of the particles and further processing in the production of bleach, detergents or cleaning agents. Moreover, the sodium percarbonate particles which have been dusted with hydrophobized silica and described in WO 95/02724 are also less readily dispersible in water and tend to form lumps and to deposit the added ones hydrophobized silica on the water surface. The use of these sodium percarbonate particles in bleaching, washing and cleaning agents therefore leads to a deterioration of the application properties of these agents.
Aufgabe der Erfindung war deshalb die Bereitstellung von Natriumpercarbonatpartikeln, die in Gegenwart von Buildern eine hohe LagerstabilitƤt aufweisen und gleichzeitig ohne Staubbildung und ohne Verbackung der Partikel gehandhabt und gelagert werden kƶnnen. Die Natriumpercarbonatpartikel mĆ¼ssen sich darĆ¼ber hinaus auch leicht und ohne RĆ¼ckstƤnde in Wasser dispergieren lassen, so dass ihre Verwendung in Bleich-, Wasch- und Reinigungsmitteln nicht zu einer Verschlechterung der Anwendungseigenschaften dieser Mittel fĆ¼hrt.The object of the invention was therefore to provide sodium percarbonate particles which have a high storage stability in the presence of builders and at the same time can be handled and stored without dust formation and without caking of the particles. In addition, the sodium percarbonate particles must also be easy to disperse in water without residues, so that their use in bleaching, washing and cleaning agents does not lead to a deterioration in the application properties of these agents.
Es wurde nun Ć¼berraschend gefunden, dass sich diese Aufgabe durch Natriumpercarbonatpartikel lƶsen lƤsst, die auf ihrer OberflƤche nur 0,01 bis 1 Gew.-% und vorzugsweise nur 0,1 bis 0,5 Gew.-% eines hydrophobierten feinteiligen Oxids aufweisen.It has now surprisingly been found that this object can be achieved by sodium percarbonate particles which have on their surface only 0.01 to 1 wt .-% and preferably only 0.1 to 0.5 wt .-% of a hydrophobized finely divided oxide.
Gegenstand der vorliegenden Erfindung sind Natriumpercarbonatpartikel, dadurch gekennzeichnet, dass sie auf ihrer OberflƤche 0,01 bis 1 Gew.-%, vorzugsweise 0,1 bis 0,5 Gew.-% eines hydrophobierten feinteiligen Oxids der Elemente Silicium, Aluminium oder Titan oder eines Mischoxids dieser Elemente enthalten, wobei das hydrophobierte feinteilige Oxid vorzugsweise eine hydrophobierte pyrogene oder gefƤllte KieselsƤure ist.The present invention relates to sodium percarbonate particles, characterized in that they contain on their surface 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of a hydrophobized finely divided oxide of the elements silicon, aluminum or titanium or a Mixed oxide contain these elements, wherein the hydrophobicized finely divided oxide is preferably a hydrophobized fumed or precipitated silica.
Die Erfindung umfasst auĆerdem ein Verfahren zur Herstellung dieser Natriumpercarbonatpartikel, dadurch gekennzeichnet, dass Natriumpercarbonatpartikel, die gegebenenfalls eine oder mehrere HĆ¼llschichten aufweisen, mit 0,01 bis 1 Gew.-%, vorzugsweise 0,1 bis 0,5 Gew.-% eines hydrophobierten feinteiligen Oxids der Elemente Silicium, Aluminium oder Titan oder eines Mischoxids dieser Elemente gemischt werden, wobei die eingesetzten Natriumpercarbonatpartikel vorzugsweise in trockenem Zustand mit dem hydrophobierten feinteiligen Oxid gemischt werden.The invention additionally encompasses a process for the preparation of these sodium percarbonate particles, which comprises sodium percarbonate particles, which optionally have one or more coating layers, with 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight, of a hydrophobized one of finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements are mixed, wherein the sodium percarbonate particles used are preferably mixed in a dry state with the hydrophobized finely divided oxide.
Die Erfindung umfasst schlieĆlich auch die Verwendung der erfindungsgemƤĆen Natriumpercarbonatpartikel als Bleichkomponente in einem Bleichmittel, Waschmittel oder Reinigungsmittel.Finally, the invention also encompasses the use of the sodium percarbonate particles according to the invention as bleaching component in a bleach, detergent or cleaning agent.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel enthalten auf ihrer OberflƤche 0,01 bis 1 Gew.-%, vorzugsweise 0,1 bis 0,5 Gew.-% eines hydrophobierten feinteiligen Oxids der Elemente Silicium, Aluminium oder Titan oder ein Mischoxid dieser Elemente. Vorzugsweise enthalten sie als hydrophobiertes feinteiliges Oxid eine hydrophobierte pyrogene oder gefƤllte KieselsƤure.The sodium percarbonate particles according to the invention contain on their surface 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of a hydrophobized finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements. Preferably, they contain as hydrophobized finely divided oxide, a hydrophobized fumed or precipitated silica.
Geeignete feinteilige Oxide sind zum Beispiel pyrogene Oxide, die durch Flammhydrolyse von flĆ¼chtigen Verbindungen der Elemente Silicium, Aluminium oder Titan oder von Mischungen dieser Verbindungen erhalten werden. Die auf diesem Weg erhƤltlichen pyrogenen Oxide oder Mischoxide weisen vorzugsweise eine mittlere PrimƤrpartikelgrƶĆe von weniger als 50 nm auf und kƶnnen zu grƶĆeren Partikeln aggregiert sein, deren mittlere PartikelgrƶĆe vorzugsweise weniger als 20 Āµm betrƤgt.Suitable finely divided oxides are, for example, pyrogenic oxides which are obtained by flame hydrolysis of volatile compounds of the elements silicon, aluminum or titanium or of mixtures of these compounds. The pyrogenic oxides or mixed oxides obtainable in this way preferably have an average primary particle size of less than 50 nm and can lead to larger particles be aggregated, the average particle size is preferably less than 20 microns.
Ebenso geeignet sind gefƤllte Oxide, die aus wƤssrigen Lƶsungen von Verbindungen der Elemente Silicium, Aluminium oder Titan oder Mischungen dieser Verbindungen ausgefƤllt wurden. Die gefƤllten Oxide, bzw. Mischoxide kƶnnen neben Silicium, Aluminium und Titan noch geringe Mengen an Alkalimetall- oder Erdalkalimetallionen enthalten. Die mittlere PartikelgrƶĆe der gefƤllten Oxide betrƤgt vorzugsweise weniger als 50 Āµm und besonders bevorzugt weniger als 20 Āµm.Also suitable are precipitated oxides which have been precipitated from aqueous solutions of compounds of the elements silicon, aluminum or titanium or mixtures of these compounds. The precipitated oxides, or mixed oxides, in addition to silicon, aluminum and titanium may still contain small amounts of alkali metal or alkaline earth metal ions. The mean particle size of the precipitated oxides is preferably less than 50 microns and more preferably less than 20 microns.
Hydrophobierte Oxide im Sinne der Erfindung sind Oxide die an ihrer OberflƤche Ć¼ber chemische Verbindungen gebundene organische Reste aufweisen und von Wasser nicht benetzt werden. Hydrophobierte Oxide kƶnnen zum Beispiel durch Umsetzen von pyrogenen oder gefƤllten Oxiden mit Organosilanen, Silazanen oder Polysiloxanen hergestellt werden. Geeignete Siliciumverbindungen zur Herstellung von hydrophobierten Oxiden sind aus EP-A 0 722 992, Seite 3, Zeile 9 bis Seite 6, Zeile 6 bekannt. Besonders bevorzugt sind hydrophobierte Oxide, die durch Umsetzung eines feinteiligen Oxids mit einer Siliciumverbindung der in EP-A 0 722 992 angefĆ¼hrten Verbindungsklassen (a) bis (e) und (k) bis (m) hergestellt wurden. Die hydrophobierten feinteiligen Oxide weisen vorzugsweise eine Methanolbenetzbarkeit von mindestens 40 auf.Hydrophobised oxides in the context of the invention are oxides which have organic radicals bound to their surface via chemical compounds and are not wetted by water. Hydrophobic oxides can be prepared, for example, by reacting fumed or precipitated oxides with organosilanes, silazanes or polysiloxanes. Suitable silicon compounds for the preparation of hydrophobized oxides are known from EP-A 0 722 992, page 3, line 9 to page 6, line 6. Hydrophoborated oxides which have been prepared by reacting a finely divided oxide with a silicon compound of the compound classes (a) to (e) and (k) to (m) mentioned in EP-A 0 722 992 are particularly preferred. The hydrophobized finely divided oxides preferably have a methanol wettability of at least 40.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel weisen vorzugsweise eine mittlere PartikelgrƶĆe im Bereich von 0,2 bis 5 mm und besonders bevorzugt im Bereich von 0,5 bis 2 mm auf. Bevorzugt werden Natriumpercarbonatpartikel mit einem geringen Feinkornanteil, vorzugsweise mit einem Anteil von weniger als 10 Gew.-% Partikel kleiner als 0,2 mm und besonders bevorzugt weniger als 10 Gew.-% Partikel mit einer PartikelgrƶĆe von weniger als 0,3 mm.The sodium percarbonate particles according to the invention preferably have an average particle size in the range from 0.2 to 5 mm and particularly preferably in the range from 0.5 to 2 mm. Preference is given to sodium percarbonate particles a low fines content, preferably with a proportion of less than 10 wt .-% particles smaller than 0.2 mm and more preferably less than 10 wt .-% of particles having a particle size of less than 0.3 mm.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel weisen vorzugsweise eine im Wesentlichen kugelfƶrmige Gestalt auf mit einer glatten OberflƤche. Partikel mit einer glatten OberflƤche weisen eine OberflƤchenrauigkeit von weniger als 10 % des Partikeldurchmessers und bevorzugt von weniger als 5 % des Partikeldurchmessers auf.The sodium percarbonate particles according to the invention preferably have a substantially spherical shape with a smooth surface. Particles with a smooth surface have a surface roughness of less than 10% of the particle diameter, and preferably less than 5% of the particle diameter.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel kƶnnen ausgehend von Natriumpercarbonatpartikeln hergestellt werden, die nach einem der bekannten Herstellverfahren fĆ¼r Natriumpercarbonat erzeugt wurden. Ein geeignetes Herstellungsverfahren fĆ¼r Natriumpercarbonat ist die Kristallisation von Natriumpercarbonat aus wƤssrigen Lƶsungen von Wasserstoffperoxid und Natriumcarbonat, wobei die Kristallisation sowohl in Gegenwart, als auch in Abwesenheit eines Aussalzungsmittels durchgefĆ¼hrt werden kann, wozu beispielhaft auf die EP-A 0 703 190 verwiesen wird. Ebenfalls geeignet ist die WirbelschichtsprĆ¼hgranulation durch AufsprĆ¼hen von wƤssriger Wasserstoffperoxidlƶsung und wƤssriger Sodalƶsung auf Natriumpercarbonatkeime in einer Wirbelschicht bei gleichzeitiger Verdampfung von Wasser, beispielhaft wird auf WO 95/06615 verwiesen. Weiterhin ist auch die Umsetzung von festen Natriumcarbonat mit einer wƤssrigen Wasserstoffperoxidlƶsung und nachfolgende Trocknung ein geeignetes Herstellverfahren. Die nach einem dieser Verfahren hergestellten Natriumpercarbonatpartikel bestehen im Wesentlichen aus Natriumcarbonatperhydrat der Zusammensetzung 2Na2CO3 Ā· 3H2O2. Sie kƶnnen darĆ¼ber hinaus noch geringe Mengen an bekannten Stabilisatoren fĆ¼r Persauerstoffverbindungen, wie z.B. Magnesiumsalze, Silikate, Phosphate und/oder Chelatkomplexbildner enthalten. Nach dem Kristallisationsverfahren in Gegenwart eines Aussalzungsmittels hergestellte Percarbonatpartikel kƶnnen darĆ¼ber hinaus auch geringe Mengen des verwendeten Aussalzungsmittels, wie z.B. Natriumchlorid enthalten. Vorzugsweise werden die erfindungsgemƤĆen Natriumpercarbonatpartikel ausgehend von Natriumpercarbonatpartikeln hergestellt, die durch WirbelschichtsprĆ¼hgranulation erhalten wurden.The sodium percarbonate particles according to the invention can be prepared starting from sodium percarbonate particles which have been produced by one of the known production processes for sodium percarbonate. A suitable production process for sodium percarbonate is the crystallization of sodium percarbonate from aqueous solutions of hydrogen peroxide and sodium carbonate, wherein the crystallization can be carried out both in the presence and in the absence of a salting out agent, by way of example reference is made to EP-A 0 703 190. Likewise suitable is the fluidized-bed spray granulation by spraying aqueous hydrogen peroxide solution and aqueous sodium carbonate solution onto sodium percarbonate nuclei in a fluidized bed with simultaneous evaporation of water, by way of example reference is made to WO 95/06615. Furthermore, the reaction of solid sodium carbonate with an aqueous hydrogen peroxide solution and subsequent drying is also a suitable production process. The sodium percarbonate particles produced by one of these processes consist essentially of sodium carbonate perhydrate of the composition 2Na 2 CO 3 .3H 2 O 2 . You can go beyond that still small amounts of known stabilizers for peroxygen compounds, such as magnesium salts, silicates, phosphates and / or chelating agents. Moreover, percarbonate particles produced by the crystallization process in the presence of a salting-out agent may also contain small amounts of the salting-out agent used, such as, for example, sodium chloride. The sodium percarbonate particles according to the invention are preferably prepared starting from sodium percarbonate particles obtained by fluidized-bed spray granulation.
In einer bevorzugten AusfĆ¼hrungsform der Erfindung weisen die Natriumpercarbonatpartikel auf einem Kern aus Natriumpercarbonat zusƤtzlich eine HĆ¼llschicht auf, die als Hauptbestandteil ein oder mehrere anorganische hydratbildende Salze enthƤlt. Das bzw. die anorganischen hydratbildenden Salze werden vorzugsweise ausgewƤhlt aus der Reihe Natriumsulfat, Natriumcarbonat, Natriumhydrogencarbonat oder Magnesiumsulfat, sowie aus Mischungen dieser Verbindungen und/oder Mischsalzen dieser Verbindungen. Besonders bevorzugt wird als anorganisches hydratbildendes Salz Natriumsulfat. In einer bevorzugten AusfĆ¼hrungsform besteht die HĆ¼llschicht im wesentlichen aus Natriumsulfat. Der Anteil dieser HĆ¼llschicht am Natriumpercarbonatpartikel liegt vorzugsweise im Bereich von 1 bis 20 Gew.-% und besonders bevorzugt im Bereich von 2 bis 10 Gew.-%, berechnet fĆ¼r die nicht-hydratisierte Form des bzw. der hydratbildenden Salze.In a preferred embodiment of the invention, the sodium percarbonate particles on a core of sodium percarbonate additionally have a coating layer which contains one or more inorganic hydrate-forming salts as the main constituent. The inorganic or hydrate-forming salts are preferably selected from the series sodium sulfate, sodium carbonate, sodium bicarbonate or magnesium sulfate, as well as mixtures of these compounds and / or mixed salts of these compounds. Particularly preferred as the inorganic hydrate-forming salt is sodium sulfate. In a preferred embodiment, the cladding layer consists essentially of sodium sulfate. The proportion of this coating layer on the sodium percarbonate particle is preferably in the range from 1 to 20% by weight and more preferably in the range from 2 to 10% by weight, calculated for the non-hydrated form of the hydrate-forming salts.
Das UmhĆ¼llen der Natriumpercarbonatpartikel erfolgt in an sich bekannter Weise. Im Prinzip werden die zu umhĆ¼llenden Partikel mit einer eine oder mehrere HĆ¼llkomponenten enthaltenden Lƶsung mƶglichst gleichmƤĆig ein oder mehrfach kontaktiert und gleichzeitig oder anschlieĆend getrocknet. Beispielsweise kann das Kontaktieren auf einem Granulierteller oder in einem Mischer, wie Taumelmischer, erfolgen. Vorzugsweise erfolgt das Beschichten durch Wirbelschichtcoating, wobei eine wƤssrige Lƶsung des bzw. der anorganischen hydratbildenden Salze auf die in einer Wirbelschicht befindlichen Natriumpercarbonatpartikel, bzw. mit einer oder mehreren Schichten umhĆ¼llten Natriumpercarbonatpartikel aufgesprĆ¼ht und gleichzeitig mit dem Wirbelschichtgas getrocknet wird. Wirbelschichtgas kann ein beliebiges Gas sein, insbesondere Luft, mit einem Verbrennungsgas direkt erhitzte Luft mit einem CO2-Gehalt im Bereich von zum Beispiel 0,1 bis etwa 15 %, reines CO2, Stickstoff und Inertgase. Besonders bevorzugt wird die HĆ¼llschicht mit dem in EP-A 0 970 917 beschriebenen Verfahren aufgebracht.The coating of the sodium percarbonate particles takes place in a manner known per se. In principle, the particles to be coated are mixed as uniformly as possible with a solution containing one or more shell components contacted and dried simultaneously or subsequently. For example, the contacting may take place on a granulating dish or in a mixer, such as a tumbling mixer. The coating is preferably carried out by fluidized-bed coating, in which case an aqueous solution of the inorganic hydrate-forming salts is sprayed onto the sodium percarbonate particles suspended in a fluidized bed or with sodium percarbonate particles coated with one or more layers and dried simultaneously with the fluidized-bed gas. Fluidized bed gas may be any gas, particularly air, air directly heated with a combustion gas having a CO 2 content in the range of, for example, 0.1 to about 15%, pure CO 2 , nitrogen and inert gases. The coating layer is particularly preferably applied by the method described in EP-A 0 970 917.
Die HĆ¼llschicht aus anorganischen hydratbildenden Salzen wird vorzugsweise so aufgebracht, dass sie den Kern aus Natriumpercarbonat vollstƤndig umschlieĆt. Beim Aufbringen der HĆ¼llschicht in Form einer wƤssrigen Lƶsung kann sich durch Anlƶsen der Natriumpercarbonatpartikel beim Beschichten an der Grenze zwischen Kernmaterial und HĆ¼llschichtmaterial ein Grenzbereich ausbilden, der neben Natriumpercarbonat und dem HĆ¼llschichtmaterial weitere Verbindungen enthalten kann. So kann dieser Grenzbereich beim Aufbringen einer HĆ¼llschicht aus im wesentlichen Natriumsulfat neben Natriumpercarbonat und Natriumsulfat noch Natriumhydrogencarbonat sowie Doppelsalze von Natriumhydrogencarbonat und Natriumsulfat wie Sesquicarbonat oder Wegscheiders Salz enthalten.The shell layer of inorganic hydrate-forming salts is preferably applied so as to completely surround the core of sodium percarbonate. When the cladding layer is applied in the form of an aqueous solution, by dissolving the sodium percarbonate particles during coating at the boundary between core material and cladding layer material, a boundary region can form which can contain other compounds in addition to sodium percarbonate and the cladding layer material. Thus, this boundary region may contain sodium hydrogen carbonate and also double salts of sodium bicarbonate and sodium sulfate such as sesquicarbonate or Wegscheiders salt when applying a coating layer of substantially sodium sulfate in addition to sodium percarbonate and sodium sulfate.
Die HĆ¼llschicht aus anorganischen hydratbildenden Salzen kann direkt auf dem Kern aus Natriumpercarbonat aufgebracht sein oder von einer oder mehreren weiteren HĆ¼llschichten unterlagert sein. ZusƤtzlich kann sie von einer oder mehreren weiteren HĆ¼llschichten Ć¼berlagert sein.The coating layer of inorganic hydrate-forming salts can be applied directly to the core of sodium percarbonate be or be underlain by one or more other enveloping layers. In addition, it may be superposed by one or more further cladding layers.
In einer weiteren bevorzugten AusfĆ¼hrungsform weisen die Natriumpercarbonatpartikel Ć¼ber einer anorganische hydratbildende Salze enthaltenden HĆ¼llschicht eine zweite HĆ¼llschicht auf, die als Hauptkomponente ein Alkalimetallsilikat mit einem Modul SiO2 zu M2O (M = Alkalimetall) von grƶĆer 2,5 enthƤlt. Besonders bevorzugt besteht die zweite HĆ¼llschicht im wesentlichen aus Alkalimetallsilikat. Unter Alkalimetallsilikat sind dabei alle Alkalimetallsilikate zu verstehen, welche im Mittel den genannten Modul ergeben. Bei dem Modul handelt es sich um das MolverhƤltnis von SiO2 zu M2O, wobei M fĆ¼r ein Alkalimetall steht und vorzugsweise Lithium, Natrium oder Kalium oder ein Gemisch dieser Alkalimetalle ist. Besonders bevorzugt ist Natriumsilikat. Der Modul des Alkalimetallsilikats liegt vorzugsweise im Bereich von 3 bis 5 und besonders bevorzugt im Bereich von 3,2 bis 4,2. Der Anteil der zweiten HĆ¼llschicht an den Natriumpercarbonatpartikeln liegt vorzugsweise im Bereich von 0,2 bis 3 Gew.-%.In a further preferred embodiment, the sodium percarbonate particles have a second coating layer containing an inorganic hydrate-forming salts, which contains as main component an alkali metal silicate with a modulus SiO 2 to M 2 O (M = alkali metal) greater than 2.5. Particularly preferably, the second cladding layer consists essentially of alkali metal silicate. Alkali metal silicate is to be understood as meaning all alkali metal silicates which give on average the abovementioned module. The modulus is the molar ratio of SiO 2 to M 2 O, where M is an alkali metal and is preferably lithium, sodium or potassium or a mixture of these alkali metals. Particularly preferred is sodium silicate. The modulus of the alkali metal silicate is preferably in the range of 3 to 5, and more preferably in the range of 3.2 to 4.2. The proportion of the second shell layer to the sodium percarbonate particles is preferably in the range of 0.2 to 3 wt .-%.
Die zweite HĆ¼llschicht wird vorzugsweise durch AufsprĆ¼hen einer Alkalimetallsilikat enthaltenden wƤssrigen Lƶsung aufgebracht, wobei bevorzugt eine wƤssrige Lƶsung mit einer Konzentration an Alkalimetallsilikat im Bereich von 2 bis 20 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% verwendet wird. Zum Aufbringen einer HĆ¼llschicht aus im wesentlichen Natriumsilikat wird vorzugsweise eine sogenannte Wasserglaslƶsung aufgesprĆ¼ht.The second coating layer is preferably applied by spraying on an aqueous solution containing alkali metal silicate, wherein preferably an aqueous solution having a concentration of alkali metal silicate in the range from 2 to 20 wt .-%, particularly preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% is used. For applying a coating layer of essentially sodium silicate, a so-called water glass solution is preferably sprayed on.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel zeigen gegenĆ¼ber vergleichbaren Natriumpercarbonatpartikeln, die an der OberflƤche kein hydrophobiertes feinteiliges Oxid enthalten, eine verbesserte LagerstabilitƤt in Gegenwart von Buildern, insbesondere in Gegenwart von silikatischen Buildern, wie z.B. Zeolithen. Bei der Stabilisierung von Natriumpercarbonatpartikeln durch eine HĆ¼llschicht aus einem anorganischen hydratbildenden Salz kann bei den erfindungsgemƤĆen Natriumpercarbonatpartikeln die gleiche LagerstabilitƤt mit einer wesentlich geringeren Menge an HĆ¼llschicht erreicht werden, als bei vergleichbaren Partikeln, die kein hydrophobiertes feinteiliges Oxid an der OberflƤche enthalten. So kƶnnen beispielsweise bei der Verwendung einer HĆ¼llschicht aus Natriumsulfat bei den erfindungsgemƤĆen Natriumpercarbonatpartikeln bereits mit einer Menge an 2 Gew.-% HĆ¼llschicht die gleichen StabilitƤten erreicht werden, wie sie bei Natriumpercarbonatpartikeln ohne hydrophobiertes feinteiliges Oxid an der OberflƤche erst mit einer HĆ¼llschichtmenge von 6 Gew.-% erzielt werden. Die erfindungsgemƤĆen Natriumpercarbonatpartikel mit einer HĆ¼llschicht aus einem anorganischen hydratbildenden Salz kƶnnen deshalb bei gleicher LagerstabilitƤt mit einem hƶheren Aktivsauerstoffgehalt hergestellt werden.The sodium percarbonate particles according to the invention exhibit improved storage stability in the presence of builders compared to comparable sodium percarbonate particles which do not contain a hydrophobized finely divided oxide on the surface, in particular in the presence of silicatic builders, e.g. Zeolites. In the stabilization of sodium percarbonate particles by a shell layer of an inorganic hydrate-forming salt, the same storage stability can be achieved with a much smaller amount of shell layer in the sodium percarbonate particles according to the invention, than with comparable particles which contain no hydrophobized finely divided oxide on the surface. Thus, for example, with the use of a coating layer of sodium sulfate in the sodium percarbonate particles according to the invention, the same stabilities can already be achieved with an amount of 2% by weight of coating layer as in the case of sodium percarbonate particles without hydrophobized finely divided oxide on the surface only with a coating layer amount of 6% by weight. -% be achieved. The sodium percarbonate particles according to the invention having a shell layer of an inorganic hydrate-forming salt can therefore be prepared with the same storage stability with a higher active oxygen content.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel weisen darĆ¼ber hinaus im Vergleich zu Partikeln, die kein hydrophobiertes feinteiliges Oxid an der OberflƤche enthalten, eine verringerte Verbackungsneigung auf, insbesondere bei der Lagerung unter Druckbelastung. Die erfindungsgemƤĆen Natriumpercarbonatpartikel sind deshalb gut silierbar, d.h. sie kƶnnen in Silos Ć¼ber lƤngere Zeit gelagert werden und zeigen auch nach lƤngerer Lagerung im Silo ein gutes FlieĆverhalten ohne Bildung von Verklumpungen oder Anbackungen im Silo. Der Vorteil der verringerten Verbackungsneigung ist besonders ausgeprƤgt bei erfindungsgemƤĆen Natriumpercarbonatpartikeln, die Ć¼ber einer ein anorganisches hydratbildendes Salz enthaltenden HĆ¼llschicht eine zweite HĆ¼llschicht aufweisen, die als Hauptkomponente ein Alkalimetallsilikat enthƤlt.In addition, the sodium percarbonate particles according to the invention have a reduced tendency to cake in comparison to particles which contain no hydrophobic finely divided oxide on the surface, in particular when stored under pressure. The sodium percarbonate particles according to the invention are therefore easy to ensile, ie they can be stored in silos for a long time and, even after prolonged storage in the silo, exhibit good flow behavior without formation of lumps or caking in the silo. The advantage of reduced tendency to cake is particularly pronounced in the case of sodium percarbonate particles according to the invention, which have a second coating layer over an outer layer containing an inorganic hydrate-forming salt, which contains an alkali metal silicate as the main component.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel zeigen im Vergleich zu den aus WO 95/02724 bekannten Partikeln mit einem GewichtsverhƤltnis von Alkalimetallpercarbonat zu hydrophoben Material im Bereich von 4:1 bis 40:1 bei der Handhabung eine deutlich geringere Staubbildung, da das hydrophobierte feinteilige Oxid bei den erfindungsgemƤĆen Natriumpercarbonatpartikeln Ć¼berraschenderweise fest an der OberflƤche der Natriumpercarbonatpartikel haftet und praktisch nicht zu Abrieb und Staubbildung beitrƤgt. Die erfindungsgemƤĆen Natriumpercarbonatpartikel kƶnnen deshalb im Gegensatz zu den aus WO 95/02724 bekannten Partikeln durch pneumatische Fƶrderung transportiert werden, ohne das es zu Staubbildung und vermehrtem Abrieb oder zur Entmischung von Natriumpercarbonat und hydrophobiertem feinteiligen Oxid kommt. Im Gegensatz zu den aus WO 95/02724 bekannten Alkalimetallpercarbonatparikeln zeigen die erfindungsgemƤĆen Natriumpercarbonatpartikel praktisch keine Nachteile bei der Dispergierbarkeit in Wasser im Vergleich zu Natriumpercarbonatpartikeln, die an der OberflƤche kein hydrophobiertes feinteiliges Oxid enthalten. Die erfindungsgemƤĆen Natriumpercarbonatpartikel lƶsen sich ebenso rasch in Wasser wie Natriumpercarbonatpartikel, die kein hydrophobiertes feinteiliges Oxid enthalten und fĆ¼hren beim Auflƶsen in Wasser in den in Bleich-, Wasch- und Reinigungsmitteln Ć¼blichen Verwendungsmengen nicht zu stƶrenden Abscheidungen des hydrophobierten feinteiligen Oxids.In comparison with the particles known from WO 95/02724 having a weight ratio of alkali metal percarbonate to hydrophobic material in the range from 4: 1 to 40: 1, the sodium percarbonate particles according to the invention exhibit a significantly lower dust formation during handling, since the hydrophobized finely divided oxide in the sodium percarbonate particles according to the invention Surprisingly firmly adheres to the surface of the sodium percarbonate particles and virtually does not contribute to abrasion and dust formation. In contrast to the particles known from WO 95/02724, the sodium percarbonate particles according to the invention can therefore be transported by pneumatic conveying, without the formation of dust and increased abrasion or segregation of sodium percarbonate and hydrophobic finely divided oxide. In contrast to the alkali metal percarbonate particles known from WO 95/02724, the sodium percarbonate particles according to the invention show virtually no disadvantages in the dispersibility in water in comparison with sodium percarbonate particles which contain no hydrophobized finely divided oxide on the surface. The sodium percarbonate particles according to the invention dissolve just as quickly in water as sodium percarbonate particles which contain no hydrophobized finely divided oxide and do not lead to disruptive precipitations of the hydrophobized finely divided oxide when dissolved in water in the usual amounts used in bleaching, washing and cleaning agents.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung der erfindungsgemƤĆen Natriumpercarbonatpartikel, bei dem Natriumpercarbonatpartikel, die gegebenenfalls eine oder mehrere HĆ¼llschichten aufweisen, mit 0,01 bis 1 Gew.-% und vorzugsweise 0,1 bis 0,5 Gew.-% eines hydrophobierten feinteiligen Oxids der Elemente Silicium, Aluminium oder Titan oder eines Mischoxids dieser Elemente gemischt werden. Als hydrophobiertes feinteiliges Oxid wird dabei vorzugsweise eine hydrophobierte pyrogene oder gefƤllte KieselsƤure verwendet.The invention furthermore relates to a process for the preparation of the sodium percarbonate particles according to the invention, in which sodium percarbonate particles optionally having one or more shell layers contain from 0.01 to 1% by weight and preferably from 0.1 to 0.5% by weight of a hydrophobicized finely divided oxide of the elements silicon, aluminum or titanium or a mixed oxide of these elements are mixed. The hydrophobized finely divided oxide used is preferably a hydrophobized pyrogenic or precipitated silica.
Die eingesetzten Natriumpercarbonatpartikel weisen vorzugsweise eine mittlere PartikelgrƶĆe im Bereich von 0,2 bis 5 mm und besonders bevorzugt im Bereich von 0,5 bis 2 mm auf. Das hydrophobierte feinteilige Oxid weist vorzugsweise eine mittlere PartikelgrƶĆe von weniger als 20 Āµm auf. Das VerhƤltnis der mittleren PartikelgrƶĆe der eingesetzten Natriumpercarbonatpartikel zur mittleren PartikelgrƶĆe des verwendeten hydrophobierten feinteiligen Oxids ist vorzugsweise grƶĆer als 20 und besonders bevorzugt grƶĆer als 50.The sodium percarbonate particles used preferably have an average particle size in the range from 0.2 to 5 mm and particularly preferably in the range from 0.5 to 2 mm. The hydrophobized finely divided oxide preferably has an average particle size of less than 20 Ī¼m. The ratio of the mean particle size of the sodium percarbonate particles used to the mean particle size of the hydrophobized finely divided oxide used is preferably greater than 20 and particularly preferably greater than 50.
Die eingesetzten Natriumpercarbonatpartikel werden vorzugsweise im trockenen Zustand mit dem hydrophobierten feinteiligen Oxid gemischt. Die Mischung kann dabei in allen zur Mischung von Feststoffen geeigneten Apparaten erfolgen. Vorzugsweise werden die Natriumpercarbonatpartikel zum Mischen mit dem hydrophobierten feinteiligen Oxid in einer Gasphase dispergiert. Der Mischvorgang kann bei dieser bevorzugten AusfĆ¼hrungsform des Verfahrens zum Beispiel in einer Wirbelschicht, in einem Fallrohr oder in einem Flugstromfƶrderer erfolgen.The sodium percarbonate particles used are preferably mixed in the dry state with the hydrophobized finely divided oxide. The mixture can be carried out in all apparatuses suitable for the mixing of solids. Preferably, the sodium percarbonate particles are dispersed in a gas phase for mixing with the hydrophobized finely divided oxide. In this preferred embodiment of the method, the mixing process can take place, for example, in a fluidized bed, in a downpipe or in a downflow conveyor.
Ćberraschenderweise wird auch beim trockenen Vermischen der Natriumpercarbonatpartikel mit 0,01 bis 1 Gew.-% des hydrophobierten feinteiligen Oxids das hydrophobierte feinteilige Oxid praktisch vollstƤndig an die OberflƤche der eingesetzten Natriumpercarbonatpartikel gebunden, so dass das eingesetzte feinteilige Oxid praktisch nicht zum Feinkornanteil und zur Staubbildung im erhaltenen Produkt beitrƤgt.Surprisingly, even when the sodium percarbonate particles are dry-mixed with from 0.01 to 1% by weight of the hydrophobized finely divided oxide, the hydrophobized finely divided oxide is almost completely bound to the surface of the sodium percarbonate particles used so that the finely divided oxide used is virtually free of fine grain and dust formation contributes to the product obtained.
Das Mischen der eingesetzten Natriumpercarbonatpartikel mit dem hydrophobierten feinteiligen Oxid in einem Fallrohr oder in einem Flugstromfƶrderer ermƶglicht in einfacher Weise die kontinuierliche Herstellung der erfindungsgemƤĆen Natriumpercarbonatpartikel und erfordert keine Mischeinrichtungen mit zusƤtzlichen bewegten Teilen. Das kontinuierliche Mischen in einem Fallrohr oder einem Flugstromfƶrderer ermƶglicht die Herstellung eines besonders homogenen Produkts, in dem im wesentlichen alle Natriumpercarbonatpartikel auf ihrer OberflƤche den erfindungsgemƤĆen Gewichtsanteil eines hydrophobierten feinteiligen Oxids aufweisen.The mixing of the sodium percarbonate particles used with the hydrophobized finely divided oxide in a downpipe or in an airflow conveyor makes it easy to continuously produce the sodium percarbonate particles according to the invention and does not require mixing devices with additional moving parts. The continuous mixing in a downpipe or a downdraft conveyor makes it possible to produce a particularly homogeneous product in which essentially all sodium percarbonate particles have on their surface the proportion by weight of a hydrophobized finely divided oxide according to the invention.
Fig.1 und Fig. 2 zeigen rasterelektronenmikroskopische Aufnahmen von erfindungsgemƤĆen Natriumpercarbonatpartikeln mit einer HĆ¼llschicht aus 6 Gew.-% Natriumsulfat, die auf der OberflƤche 0,5 Gew.-% der hydrophobierten KieselsƤure AerosilĀ® R812 enthalten. Die Partikel wurden durch WirbelschichtsprĆ¼hgranulation, anschlieĆende UmhĆ¼llung durch AufsprĆ¼hen von Natriumsulfatlƶsung in einer Wirbelschicht unter Verdampfung von Wasser und trockenes Mischen der umhĆ¼llten Partikel mit der hydrophobierten KieselsƤure in einem Taumelmischer hergestellt. Die Abbildungen zeigen, dass in den erfindungsgemƤĆen Partikeln die hydrophobierte KieselsƤure praktisch vollstƤndig an der OberflƤche der eingesetzten Natriumpercarbonatpartikel haftet.1 and 2 show scanning electron micrographs of sodium percarbonate particles according to the invention with a coating layer of 6% by weight of sodium sulfate, which contain 0.5% by weight of the hydrophobized silica AerosilĀ® R812 on the surface. The particles were prepared by fluidized bed spray granulation followed by coating by spraying sodium sulfate solution in a fluidized bed to evaporate water and dry mixing the coated particles with the hydrophobized silica in a tumble mixer. The Figures show that in the particles according to the invention the hydrophobized silica adheres almost completely to the surface of the sodium percarbonate particles used.
Ein weiterer Gegenstand der Erfindung richtet sich auf die Verwendung der erfindungsgemƤĆen Natriumpercarbonatpartikeln als bleichwirksame Komponente, in Wasch-, Bleich- oder Reinigungsmitteln. Bei den Wasch-, Bleich- oder Reinigungsmitteln handelt es sich insbesondere um solche, welche mindestens einen Builder und vorzugsweise einen silikatischen Builder enthalten. Unter Builder werden dabei alle lƶslichen oder unlƶslichen Verbindungen verstanden, die bei der Verwendung des Wasch-, Bleich- oder Reinigungsmittels in der Lage sind, Calcium- und/oder Magnesiumionen aus dem verwendeten Wasser zu sequestrieren, bzw. zu komplexieren. Beispiele fĆ¼r silikatische Builder sind lƶsliche Silikate, unlƶsliche Schichtsilikate und Zeolithe, insbesondere Zeolith A und Zeolith X.Another object of the invention is directed to the use of sodium percarbonate according to the invention as a bleach-active component, in detergents, bleaches or cleaning agents. The washing, bleaching or cleaning agents are in particular those which contain at least one builder and preferably a silicate builder. Builders are understood to be all soluble or insoluble compounds which, when using the washing, bleaching or cleaning agent, are capable of sequestering or complexing calcium and / or magnesium ions from the water used. Examples of silicate builders are soluble silicates, insoluble phyllosilicates and zeolites, in particular zeolite A and zeolite X.
Die erfindungsgemƤĆen Natriumpercarbonatpartikel werden in Wasch-, Bleich- oder Reinigungsmitteln vorzugsweise in einer Menge von 5 bis 50 Gew.-%, besonders bevorzugt 10 bis 40 Gew.-% und insbesondere 15 bis 20 Gew.-% verwendet. Die Wasch-, Bleich- und Reinigungsmittel kƶnnen neben dem erfindungsgemƤĆen Natriumpercarbonatpartikeln weitere Bestandteile enthalten, insbesondere
- ein oder mehrere Tenside, vorzugsweise ausgewƤhlt aus der Reihe der kationischen, anionischen, nicht-ionischen und amphoteren Tenside,
- einen oder mehrere anorganische und/oder organische Builder, vorzugsweise ausgewƤhlt aus der Reihe der Zeolithe, Schichtsilikate, lƶslichen Silikate, Polyphosphate, AminopolyessigsƤuren, AminopolyphosphonsƤuren sowie PolyoxycarbonsƤuren,
- eine oder mehrere alkalisch wirkende Komponenten, vorzugsweise ausgewƤhlt aus der Reihe der Alkalicarbonate, Alkalisilikate und Alkanolamine,
- einen oder mehrere Bleichaktivatoren, vorzugsweise ausgewƤhlt aus der Reihe der N-Acylverbindungen und O-Acylverbindungen, wie zum Beispiel Tetraacetylethylendiamin (TAED) oder Nonanoyloxybenzolsulfonat (NOBS),
- ein oder mehrere Enzyme, vorzugsweise ausgewƤhlt aus der Reihe der Lipasen, Cutinasen, Amylasen, Proteasen, Esterasen, Cellulasen, Pectinasen, Lactasen und Peroxidasen und
- einen oder mehrere Hilfsstoffe, vorzugsweise ausgewƤhlt aus der Reihe der Peroxidstabilisatoren, Antiredepositionsmittel, optischen Aufheller, Schauminhibitoren, Desinfektionsmittel, Korrosionsinhibitoren, Duftstoffe und Farbstoffe.
- one or more surfactants, preferably selected from the group of cationic, anionic, nonionic and amphoteric surfactants,
- one or more inorganic and / or organic builders, preferably selected from the series of zeolites, phyllosilicates, soluble silicates, Polyphosphates, aminopolyacetic acids, aminopolyphosphonic acids and polyoxycarboxylic acids,
- one or more alkaline components, preferably selected from the group of alkali metal carbonates, alkali metal silicates and alkanolamines,
- one or more bleach activators, preferably selected from the series of N-acyl compounds and O-acyl compounds, such as, for example, tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS),
- one or more enzymes, preferably selected from the group of lipases, cutinases, amylases, proteases, esterases, cellulases, pectinases, lactases and peroxidases and
- one or more excipients, preferably selected from the series of peroxide stabilizers, anti redeposition agents, optical brighteners, foam inhibitors, disinfectants, corrosion inhibitors, fragrances and dyes.
Durch die Verwendung der erfindungsgemƤĆen Natriumpercarbonatpartikel als bleichwirksame Komponente, in Wasch-, Bleich- oder Reinigungsmitteln lƤĆt sich die LagerstabilitƤt dieser Mittel verbessern und der Verlust an Aktivsauerstoff bei der Lagerung der Mittel verringern.The use of the sodium percarbonate particles according to the invention as a bleach-acting component in detergents, bleaches or cleaners improves the storage stability of these compositions and reduces the loss of active oxygen during storage of the compositions.
Das in den Beispielen zur Herstellung der erfindungsgemƤĆen Natriumpercarbonatpartikel eingesetzte Natriumpercarbonat wurde durch Wirbelschichtaufbaugranulation nach dem in WO 95/06615 beschriebenen Verfahren hergestellt. Die eingesetzten Natriumpercarbonatpartikel wiesen eine mittlere PartikelgrƶĆe von 0,65 mm auf und enthielten praktisch keine Partikel mit einem Durchmesser kleiner 0,3 mm. Natriumpercarbonatpartikel mit einer HĆ¼llschicht aus 2 Gew.-% Natriumsulfat wurden daraus in einer Laborapparatur durch AufsprĆ¼hen von wƤssriger Natriumsulfatlƶsung und gleichzeitiges Verdampfen von Wasser hergestellt. Natriumpercarbonatpartikel mit einer HĆ¼llschicht aus 6 Gew.-% Natriumsulfat wurden durch AufsprĆ¼hen einer wƤssrigen Natriumsulfatlƶsung nach dem in EP-A 0 670 917 beschriebenen Verfahren hergestellt.The sodium percarbonate used in the examples for the preparation of the sodium percarbonate particles according to the invention was prepared by fluidized-bed granulation according to the process described in WO 95/06615. The sodium percarbonate particles used had a mean particle size of 0.65 mm and contained virtually no particles with a diameter of less than 0.3 mm. Sodium percarbonate particles having a coating layer of 2% by weight of sodium sulfate were prepared therefrom in a laboratory apparatus by spraying aqueous sodium sulfate solution and simultaneously evaporating water. Sodium percarbonate particles with a coating layer of 6% by weight sodium sulfate were prepared by spraying an aqueous sodium sulfate solution according to the method described in EP-A 0 670 917.
Zur Herstellung der erfindungsgemƤĆen Natriumpercarbonatpartikel wurde das eingesetzte Natriumpercarbonat in einem Taumelmischer 30 min mit den in Tabellen 1 bis 3 und Tabelle 5 angefĆ¼hrten Mengen und Typen an feinteiliger KieselsƤure gemischt. Die verwendeten feinteiligen KieselsƤuren wiesen folgende Eigenschaften auf:
- AerosilĀ® R812: pyrogene KieselsƤure, hydrophobiert mit Hexamethyldisilazan, spezifische OberflƤche nach BET 260 m2/g, mittlere PrimƤrpartikelgrƶĆe 7 nm, Methanolbenetzbarkeit 50
- AerosilĀ® R972: pyrogene KieselsƤure, hydrophobiert mit Dimethyldichlorsilan, spezifische OberflƤche nach BET 110 m2/g, mittlere PrimƤrpartikelgrƶĆe 16 nm, Methanolbenetzbarkeit 35
- AerosilĀ® 200: pyrogene KieselsƤure, nicht modifiziert, spezifische OberflƤche nach BET 200 m2/g, mittlere PrimƤrpartikelgrƶĆe 12 nm
- SipernatĀ® D17: gefƤllte KieselsƤure, hydrophobiert, spezifische OberflƤche nach BET 100 m2/g, mittlere PartikelgrƶĆe 7,0 Āµm, Methanolbenetzbarkeit 55
- SipernatĀ® 22S: gefƤllte KieselsƤure, nicht modifiziert, spezifische OberflƤche nach BET 190 m2/g, mittlere PartikelgrƶĆe 7,0 Āµm
- AerosilĀ® R812: fumed silica, hydrophobed with hexamethyldisilazane, BET specific surface area 260 m 2 / g, mean primary particle size 7 nm, methanol wettability 50
- AerosilĀ® R972: fumed silica, hydrophobed with dimethyldichlorosilane, specific surface area according to BET 110 m 2 / g, average primary particle size 16 nm, methanol wettability 35
- AerosilĀ® 200: fumed silica, not modified, BET specific surface area 200 m 2 / g, mean primary particle size 12 nm
- SipernatĀ® D17: precipitated silica, hydrophobed, BET specific surface area 100 m 2 / g, mean particle size 7.0 Ī¼m, methanol wettability 55
- SipernatĀ® 22S: precipitated silica, not modified, BET specific surface area 190 m 2 / g, mean particle size 7.0 Ī¼m
Zur Bestimmung der LagerstabilitƤt in Gegenwart von zeolithischem Builder wurden 15 g des erhaltenen Produkts mit 15 g Zeolith A (Zeocros CG 180) gemischt und fĆ¼r 68 h bei 38Ā°C und 75 % relativer Feuchte offen in einem Klimaschrank gelagert. Vor und nach der Lagerung wurde der Aktivsauerstoffgehalt durch manganometrische Titration bestimmt und daraus der Aktivsauerstoffgehalt bei der Lagerung (rel. Rest-Oa) berechnet. Die Versuchsergebnisse sind in den Tabellen 1 bis 3 zusammengestellt und zeigen, dass die erfindungsgemƤĆen Natriumpercarbonatpartikel eine deutlich bessere LagerstabilitƤt in Gegenwart von zeolithischen Buildern aufweisen als Natriumpercarbonatpartikel, die an ihrer OberflƤche kein feinteiliges Oxid oder eine feinteilige hydrophile KieselsƤure, wie AerosilĀ® 200 oder SipernatĀ® 22S enthalten.
In Tabelle 4 sind fĆ¼r einige der hergestellten Natriumpercarbonatpartikel die Aktivsauerstoffgehalte und die Handhabungseigenschaften der Lƶsezeit und des Abriebs zusammengestellt. Die Aktivsauerstoffgehalte wurden durch manganometrische Titration bestimmt. Die Lƶsezeit wurde konduktometrisch bestimmt als die Zeit, nach der beim Auflƶsen von 2,5 g Produkt pro Liter Wasser bei 20Ā°C unter RĆ¼hren 90 % des Endwerts der LeitfƤhigkeit erreicht werden. Der Abrieb wurde nach ISO 5937 bestimmt. Das Produkt aus den Beispielen 6, 10, 16 und 18 zeigte bei der Bestimmung der Lƶsezeit keine Tendenz zur Verklumpung und lieferte klare Lƶsungen. Das Produkt aus Beispiel 19 verklumpte bei der Bestimmung der Lƶsezeit und zeigte auch nach vollstƤndiger Auflƶsung des Natriumpercarbonats auf der OberflƤche der Lƶsung eine sichtbare Abscheidung der hydrophoben KieselsƤure.
Aus den Daten von Tabelle 4 ist ersichtlich, dass sich die erfindungsgemƤĆen Natriumpercarbonatpartikel (Beispiel 10) von vergleichbaren Natriumpercarbonatpartikeln (Beispiel 6), die an der OberflƤche kein feinteiliges Oxid aufweisen, hinsichtlich der Auflƶsung in Wasser und der Staubbildung durch Abrieb nicht unterscheiden. Ein nach WO 95/02724 hergestelltes Produkt (Beispiel 19) zeigt dagegen eine deutlich hƶhere Staubbildung durch Abrieb, sowie eine verlƤngerte Lƶsezeit, wobei es beim Auflƶsen der Partikel zur Verklumpung kommt und auch nach Auflƶsen des Natriumpercarbonats unerwĆ¼nschte Abscheidungen der im Produkt enthaltenen KieselsƤure auftreten.From the data of Table 4 it can be seen that the sodium percarbonate particles according to the invention (Example 10) of comparable sodium percarbonate particles (Example 6), which have no finely divided oxide on the surface, do not differ in terms of dissolution in water and dust formation due to attrition. In contrast, a product prepared according to WO 95/02724 (Example 19) shows a significantly higher dust formation by abrasion, as well as a prolonged dissolution time, whereby clumping occurs on dissolution of the particles and unwanted deposits of the silica contained in the product occur even after dissolution of the sodium percarbonate.
Tabelle 5 zeigt durch Siebanalysen bestimmte KorngrƶĆenverteilungen der Proben aus den Beispielen 6 und 10, wobei sich die Probe aus Beispiel 10 von der Probe aus Beispiel 6 nur durch das Aufbringen von 0,3 Gew.-% AerosilĀ® R812 unterscheidet. Das Fehlen von Feinkorn im Bereich kleiner 0,3 mm zeigt, dass das aufgebrachte AerosilĀ® an der OberflƤche der Natriumpercarbonatpartikel haftet.
Von den Proben der Beispiele 15, 18 und 19 wurde auĆerdem die Silierbarkeit durch Messung des Zeitverfestigungsverhaltens nach Jenike bestimmt, wie in EP-B 863 842 auf Seite 5, Zeilen 20 bis 38 beschrieben. Der FlieĆfƤhigkeitsindex ffc ist ein MaĆ fĆ¼r die FlieĆfƤhigkeit des Materials nach Lagerung unter Druckbelastung, wie sie bei Lagerung in einem Silo erfolgt. Materialien mit einem hƶheren FlieĆfƤhigkeitsindex ffc zeigen eine geringere Zeitverfestigung und weniger Verbackungen und sind auch nach lƤngerer Lagerung in einem Silo noch frei flieĆfƤhig. Die in Tabelle 6 zusammengestellten Ergebnisse zeigen, dass die erfindungsgemƤĆen Natriumpercarbonatpartikel (Beispiel 18) im Vergleich mit Natriumpercarbonatpartikeln (Beispiel 15), die an der OberflƤche kein feinteiliges Oxid aufweisen, weniger Zeitverfestigung und damit eine verbesserte FlieĆfƤhigkeit und Silierbarkeit aufweisen, wƤhrend ein nach WO 95/02724 hergestelltes Produkt (Beispiel 19) eine hƶhere Zeitverfestigung und damit eine verschlechterte FlieĆfƤhigkeit und Silierbarkeit aufweist.
In Tabelle 7 sind die Ergebnisse von Klimatests zur Bestimmung der LagerstabilitƤt von Natriumpercarbonat in einem handelsĆ¼blichen Vollwaschmittel zusammengestellt. Im Klimatest wird das Natriumpercarbonat mit einem phosphatfreien, zeolithhaltigen Waschmittelpulver und mit Aktivator TAED in einer solchen Menge gemischt, dass das Gemisch 5 Gew.-% TAED enthƤlt und der Aktivsauerstoffgehalt des Gemischs etwa 2,35 Gew.-% betrƤgt. Das Waschmittelpulver enthƤlt als Bestandteile (in Gew.-%)
Beispiel 20 wurde mit einem Natriumpercarbonat durchgefĆ¼hrt, das eine HĆ¼llschicht aus 6 Gew.-% Natriumsulfat und eine PartikelgrƶĆe von mehr als 0,4 mm aufweist. Beispiel 21 wurde mit erfindungsgemƤĆen Natriumpercarbonatpartikeln ausgefĆ¼hrt, bei denen, wie oben beschrieben, auf die Natriumpercarbonatpartikel von Beispiel 20 0,5 Gew.-% der hydrophobierten KieselsƤure AerosilĀ® R812 aufgebracht waren.
Die Ergebnisse aus Tabelle 7 zeigen, dass die erfindungsgemƤĆen Natriumpercarbonatpartikel im Vergleich zu Natriumpercarbonat, dass an der OberflƤche kein feinteiliges, hydrophobiertes Oxid aufweist, bei der Verwendung als Bleichkomponente in einem Waschmittel zu einem verringerten Verlust an Aktivsauerstoffgehalt bei der Lagerung des Waschmittels fĆ¼hren.The results of Table 7 show that the sodium percarbonate particles of the present invention, when used as a bleaching component in a detergent, lead to a reduced loss of active oxygen content during storage of the detergent compared to sodium percarbonate having no finely divided, hydrophobized oxide on the surface.
Claims (17)
- Sodium percarbonate particles,
characterized in that
they comprise on their surface 0.01 to 1 wt%, preferably 0.1 to 0.5 wt%, of a hydrophobized finely divided oxide of the elements Si, Al or Ti or a mixed oxide of these elements. - Sodium percarbonate particles according to Claim 1,
characterized in that
said hydrophobized finely divided oxide is a hydrophobized pyrogenic or precipitated silica. - Sodium percarbonate particles according to Claim 1 or 2,
characterized in that
said hydrophobized finely divided oxide has an average particle size of less than 20 Āµm. - Sodium percarbonate particles according to one of the preceding claims,
characterized in that
said sodium percarbonate particles have an average particle size in the range of from 0.2 to 5 mm, preferably in the range of from 0.5 to 2 mm. - Sodium percarbonate particles according to one of the preceding claims,
characterized in that
said sodium percarbonate particles have an essentially spherical shape with a smooth surface. - Sodium percarbonate particles according to one of the preceding claims,
characterized in that
said sodium percarbonate particles have been prepared by fluidized bed spray granulation. - Sodium percarbonate particles according to one of the preceding claims,
characterized in that
each sodium percarbonate particle is surrounded by a coating, said coating comprising one or more hydrate-forming inorganic salts as the main component(s) on a core of sodium percarbonate. - Sodium percarbonate particles according to Claim 7,
characterized in that
said one or more hydrate-forming inorganic salts are selected from the group consisting of: sodium sulphate, sodium carbonate, sodium hydrogencarbonate or magnesium sulphate, as well as mixtures or mixed salts of these compounds, and is preferably sodium sulphate. - Sodium percarbonate particles according to Claim 7 or 8,
characterized in that
the proportion of said coating layer in the sodium percarbonate particle is in the range of from 1 to 20 wt% and preferably in the range of from 2 to 10 wt%. - Sodium percarbonate particles according to one of Claims 7 to 9,
characterized in that
they further comprise a second coating over said coating comprising hydrate-forming inorganic salts, said second coating comprising as its main component an alkali metal silicate with a modulus SiO2 to M2O (M = alkali metal) of greater than 2.5. - Sodium percarbonate particles according to Claim 10,
characterized in that
said second coating is prepared by spraying on an aqueous solution comprising said alkali metal silicate with an alkali metal silicate content in the range of from 2 to 20 wt%. - Process for producing sodium percarbonate particles according to one of Claims 1 to 11,
characterized in that
sodium percarbonate particles, optionally having one or more coatings, are mixed with 0.01 to 1 wt%, preferably 0.1 to 0.5 wt%, of a hydrophobized finely divided oxide of the elements Si, Al or Ti or a mixed oxide of these elements. - Process according to Claim 12,
characterized in that
said sodium percarbonate particles are mixed with said hydrophobized finely divided oxide in the dry state. - Process according to Claim 12 or 13,
characterized in that
said sodium percarbonate particles have an average particle size in the range of from 0.2 to 5 mm, preferably in the range of from 0.5 to 2 mm, and said hydrophobized finely divided oxide has an average particle size of less than 20 Āµm. - Process according to one of Claims 12 to 14,
characterized in that
said sodium percarbonate particles are dispersed in a gas phase for mixing with said hydrophobized finely divided oxide. - Process according to Claim 15,
characterized in that
said hydrophobized finely divided oxide is mixed with said sodium percarbonate particles in a falling tube or in an entrained-bed conveyor. - Use of sodium percarbonate particles according to one of Claims 1 to 11 as a bleach component in a bleach composition, detergent composition or cleanser composition.
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| SI200330595T SI1572855T1 (en) | 2002-12-20 | 2003-12-18 | Sodium percarbonate particles with improved storage stability |
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| DE10261161 | 2002-12-20 | ||
| PCT/EP2003/014445 WO2004058932A1 (en) | 2002-12-20 | 2003-12-18 | Sodium percarbonate particles with improved storage stability |
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| EP (1) | EP1572855B1 (en) |
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| MXPA05006452A (en) | 2002-12-20 | 2005-08-19 | Degussa | Liquid detergent and cleaning agent composition. |
| DE50300760D1 (en) | 2003-05-07 | 2005-08-18 | Degussa | Enveloped sodium percarbonate granules with improved storage stability |
| EP1628912A2 (en) * | 2003-05-23 | 2006-03-01 | Degussa AG | Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen |
| DE102004054495A1 (en) * | 2004-11-11 | 2006-05-24 | Degussa Ag | Sodium percarbonate particles with a thiosulfate containing shell layer |
| ES2314833T3 (en) * | 2006-07-27 | 2009-03-16 | Evonik Degussa Gmbh | PARTICLES WRAPPED BY SODIUM PERCARBONATE. |
| ES2317433T3 (en) * | 2006-07-27 | 2009-04-16 | Evonik Degussa Gmbh | PARTICLES WRAPPED BY SODIUM PERCARBONATE. |
| DE502006006898D1 (en) | 2006-07-27 | 2010-06-17 | Evonik Degussa Gmbh | Encased sodium percarbonate particles |
| EP1905738A1 (en) * | 2006-09-28 | 2008-04-02 | Evonik Degussa GmbH | Process for preparing granular sodium percarbonate |
| DE502007005869D1 (en) | 2007-12-19 | 2011-01-13 | Evonik Degussa Gmbh | Process for the preparation of coated sodium percarbonate particles |
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| US8476216B2 (en) * | 2010-05-28 | 2013-07-02 | Milliken & Company | Colored speckles having delayed release properties |
| CN101857239B (en) * | 2010-06-08 | 2012-05-23 | å¦éØå¤§å¦ | Preparation method of composite hollow silicate |
| US20140179585A1 (en) * | 2012-12-20 | 2014-06-26 | The Procter & Gamble Company | Detergent composition with silicate coated bleach |
| CN105722791B (en) * | 2013-11-15 | 2018-01-26 | ä½åéå±ēæå±±ę Ŗå¼ä¼ē¤¾ | Method for producing surface-treated oxide particles and oxide particles obtained by the method |
| WO2015166942A1 (en) * | 2014-04-28 | 2015-11-05 | ę Ŗå¼ä¼ē¤¾čę | In-bath treatment composition |
| EP3034551A1 (en) * | 2014-12-17 | 2016-06-22 | Akzo Nobel Chemicals International B.V. | Powder mixture comprising organic peroxide |
| CN108342258B (en) * | 2017-01-25 | 2022-04-01 | č±ēę Ŗå¼ä¼ē¤¾ | Liquid detergent composition |
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2003
- 2003-05-07 DE DE10320197A patent/DE10320197A1/en not_active Withdrawn
- 2003-05-07 DE DE10320196A patent/DE10320196A1/en not_active Withdrawn
- 2003-12-02 DE DE60309070T patent/DE60309070T2/en not_active Expired - Lifetime
- 2003-12-02 CN CNB200380107004XA patent/CN100562562C/en not_active Expired - Fee Related
- 2003-12-11 CN CNB2003801069288A patent/CN100519719C/en not_active Expired - Fee Related
- 2003-12-18 PL PL377440A patent/PL377440A1/en unknown
- 2003-12-18 AU AU2003296668A patent/AU2003296668A1/en not_active Abandoned
- 2003-12-18 ES ES03813896T patent/ES2274322T3/en not_active Expired - Lifetime
- 2003-12-18 BR BR0317444-1A patent/BR0317444A/en not_active IP Right Cessation
- 2003-12-18 JP JP2004562779A patent/JP2006510564A/en not_active Withdrawn
- 2003-12-18 CA CA002511022A patent/CA2511022A1/en not_active Abandoned
- 2003-12-18 KR KR1020057011627A patent/KR20050089975A/en not_active Ceased
- 2003-12-18 MX MXPA05006455A patent/MXPA05006455A/en unknown
- 2003-12-18 WO PCT/EP2003/014445 patent/WO2004058932A1/en not_active Ceased
- 2003-12-18 AT AT03813896T patent/ATE341606T1/en not_active IP Right Cessation
- 2003-12-18 RU RU2005122906/15A patent/RU2337135C2/en not_active IP Right Cessation
- 2003-12-18 DE DE50305305T patent/DE50305305D1/en not_active Expired - Lifetime
- 2003-12-18 CN CNB2003801070035A patent/CN1323148C/en not_active Expired - Fee Related
- 2003-12-18 EP EP03813896A patent/EP1572855B1/en not_active Expired - Lifetime
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- 2005-06-16 US US11/155,918 patent/US20060014658A1/en not_active Abandoned
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| ES2274322T3 (en) | 2007-05-16 |
| AU2003296668A1 (en) | 2004-07-22 |
| CN1729281A (en) | 2006-02-01 |
| DE60309070D1 (en) | 2006-11-23 |
| ATE341606T1 (en) | 2006-10-15 |
| DE10320197A1 (en) | 2004-07-08 |
| DE60309070T2 (en) | 2007-05-16 |
| CN1323148C (en) | 2007-06-27 |
| CN100519719C (en) | 2009-07-29 |
| EP1572855A1 (en) | 2005-09-14 |
| DE50305305D1 (en) | 2006-11-16 |
| KR20050089975A (en) | 2005-09-09 |
| DE10320196A1 (en) | 2004-07-08 |
| RU2005122906A (en) | 2007-01-27 |
| JP2006510564A (en) | 2006-03-30 |
| US20060014658A1 (en) | 2006-01-19 |
| CN1729282A (en) | 2006-02-01 |
| WO2004058932A1 (en) | 2004-07-15 |
| CN1729283A (en) | 2006-02-01 |
| CA2511022A1 (en) | 2004-07-15 |
| PL377440A1 (en) | 2006-02-06 |
| CN100562562C (en) | 2009-11-25 |
| MXPA05006455A (en) | 2005-08-19 |
| BR0317444A (en) | 2005-11-16 |
| RU2337135C2 (en) | 2008-10-27 |
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